Certain phosphinooxyphthalide compounds



United States Patent 3,494,937 CERTAIN PHOSPHINOOXYPHTHALIDE COMPOUNDSGraham 0. Osborne, Christchurch, South Island, New

Zealand, and Shirley B. Webb and Jack Wood, Sittingboume, Kent, England,assignors to Shell Oil Company, New York, N.Y., a corporation ofDelaware No Drawing. Filed Sept. 26, 1966, Ser. No. 581,691 Claimspriority, application Great Britain, Oct. 1, 1965, 41,722/ 65 Int. Cl.C07d 5/36; C07f 9/16; A01n 9/36 US. Cl. 260-3433 8 Claims ABSTRACT OFTHE DISCLOSURE Compounds of the formula:

where R, R, R", R, X, Z and n are as defined as hereinafter are usefulas insecticides.

This invention relates to novel organophosphorus compounds, toinsecticidal compositions containing them, and to the use of saidcompounds and compositions in combatting insect pests, and in protectingornamental and crop plants from attack by insects.

The novel compounds of the invention can be represented by the generalformula:

wherein R and R each independently represents lower alkoxy, middlehalogensubstituted lower alkoxy, lower alkenyloxy, amino (NH alkylordialkyl-IO amino, lower alkoxyalkoxy and lower alkoxycarbonylalkoxy,each alkyl (or alkenyl) moiety preferably containing 1 to 4 carbonatoms; R" and R each independently represents hydrogen, alkyl or (middlehalo)alkyl, preferably containing from 1 to 4 carbon atoms, or R and Rtogether can represent lower alkylidene, preferably which contains from1 to 4 carbon atoms, and which may be substituted by middle halogen; Xrepresents oxygen or sulfur; Y represents oxygen or sulfur; Z representsalkoxy of from 1 to 4 carbon atoms or middle halogen; n is zero, 1, 2 or3.

Alkyl and/or alkenyl moieties involved in the structure may bebranched-chain or straight-chain in configuration. By middle halogen ismeant bromine or chlorine. When R" and R together represent analkylidene group (R and R each being one of and together constitutingthe olefinic double bond to the indicated ring carbon atom), preferablythe alkylidene group is methylene, and if substituted by halogenpreferably is dichloromethylene.

Preferred compounds of the invention are those in which R" and R each ishydrogen, methyl or together form the dichloromethylene group, R and/orR each is methoxy, ethoxy, isopropoxy, dimethylamino, allyloxymethoxyethoxy, ethoxycarbonylmethoxy, n is O, 1 or 2 and Z is chlorine,bromine or methoxy.

Most preferred are the compounds of this subclass wherein R and R eachis unsubstituted alkoxy of 1 to 3 3,494,937 Patented F eb. 10, 1970 "Icecarbon atoms, R and R each is hydrogen, X is sulfur, Y is oxygen orsulfur and n is zero.

The compounds 5-dimethoxyphosphinothioyloxyphthalide,5-dimethoxyphosphinothioyloxy-l-thiophthalide, 5-diethoxyphosphinothioyloxy-l-thiophthalide, and 5-[methoxy (2methoxyethoxy)phosphinothioyloxy]phthalide are particularly effective asinsecticides and accordingly are preferred compounds of the invention.

The phthalides of the invention may be prepared by a process whichcomprises reacting under basic conditions a phenol of the followinggeneral formula:

or an alkali metal salt thereof, with a halide of the following generalformula:

P-hal R! where R, R, R", R, X, Y, Z and n have the meanings aforesaidand hal represents a middle halogen atom. The basic conditions for thereaction may be produced where necessary by the addition of a base. Whena base is added it may be a nitrogenous base, e.g. trimethylamine orpreferably an alkali or alkaline earth metal carbonate, e.g. sodium orpotassium carbonate.

The reaction is preferably carried out in an inert liquid reactionmedium, which may be a solvent for the reactants or for the products ofthe reaction, or both. Inert reaction media such as acetone and methylisobutyl ketone are esecially suitable for this purpose; other reactionmedia such as benzene, diethyl ether, chloroform and tetrahydrofuran aresuitable.

The reaction may be carried out at a temperature in the range 0-150 C.,preferably between 50 C. and 100 C.

The hydroxyphthalides, used as starting materials in the above process,may be prepared according to methods disclosed in J.C.S., 867-871(1931); Bull. Soc. Sci. Bretagne, 26, 7122 (1951) and J. Ind. Chem.Soc., 40, 239-240, 1963. The hydroxythiophthalides may be prepared bythe action of phosphorus pentasulfides on an acetoxyphthalide withsubsequent hydrolysis to give the sodium salt of thehydroxyl-l-thiophthalide. Phosphorylation may then be carried outwithout isolation of the intermediate hydroxythiophthalide.

The compounds of the invention, their preparation and their insecticidalactivity are further illustrated in the Examples that follow in whichparts by weight (w.) and parts by volume (v.) bear the same relation asthe kilogram to the litre.

EXAMPLE I Preparation of 5-dimethoxyphosphinothioyloxyphthalide Amixture of S-hydroxyphthalide (1.5 w.),dimethylphosphorochloridothionate (1.6 w.) and anhydrous potassiumcarbonate (0.86 w.), was heated under reflux with dry methyl isobutylketone v.) for 5 hours. After cooling the reaction mixture was filteredand the solvent was evaporated under reduced pressure. The liquidresidue was taken up in methylene chloride, washed with cold aqueous(0.2 N) sodium hydroxide solution (25 v.) followed by cold water anddried over anhydrous magnesium sulfate. After filtration, the solventwas removed under reduced pressure. Recrystallization from hexane gavecolorless crystals of 5-dimethoxyphosphinothioyloxyphthalide. M.P.59.56l.5 C. Yield 63%.

3 Analysis (percent by weight).Found: C, 43.6; H, 4.0; S, 11.8; P, 11.0.C H PSO requires: C, 43.8; H, 4.0; S, 11.7; P, 11.3.

4 with methyl (dimethylamino)phosphorochloridothionate (5.5 w.) at 95 C.for 6 hours.

After cooling the solvent was removed under reduced EXAMPLE II pressure,the residue taken up in ether, the ether solution Preparation of4-bromo-5-dimethoxyphosphinothioyl- 5 3332519532 5 2 g; i g f igfi d zjd i g th h d d d turated with a in ixturz of zh lorofjrris irbon tet izlzhloi i f was g {3f d 51 ride (1:1). Evaporation of the solventmixture resulted m Xa p e l y roxyp e an y in an oil which crystallizedon standing. Further crystalphpsphofiochlordothionate were used asstarting mate- 10 lization from aqueous alcohol (1.1) gave s [methoxyria s. T e pro not obtained was 4-bromo-5-dimethoxyuneth lammo hoshmoth1o 1 th1o hthalide MP. 58 phosphmothloyloxyphthalide. M.P. 77-79 C.Yield 44%. 2 C y )p p y 1 P P g s g g q g 3 Analysis (percent byweight).Found: C, 46.3; H, 3 5 I requresa 5.0; N, 4.7. C H O PSNrequires: c, 46.0; H, 4.9;

EXAMPLE III I EXAMPLE V Preparatlon of 5'dullethoxyfihosphmothloyloxy'1'The compounds shown in Table 1 were prepared in a thlophtha manneranalogous to that described in Examples I-IV. A solution of 1% sodiumethoxide 1n ethanol (11.5 v.) EXAMPLE VI was added to a cold solution of5-acetoxy-1-thiophthalide h f 1 04 in absolute alcohol (65 The sodiumsalt of This example 1 ustratest e preparation 0 an emu :11 a;5-hydroxy-l-thiophthalide was obtained by removing the ble Concentrate 9confamlgg a compoun o solvent under reduced pressure at a temperaturenot exthe Present mvennon as actfve f ceeding 40 C. This product wastaken up in acetone and The p nents were dlSSO vedfilln tde propor 10118refluxed for 15 minutes with 0,0-dimethyl phosphoro- Shown and thesohmonb ended and tare W chloridothionate (0.8 w.). After cooling, themixture was filtered and the solvent was removed by evaporation un-5'd1n 1ethXyPhSphmothloyloxy'l'thlophthahde der reduced pressure.TensfofiX AS 9 The product, 5-dimethoxyphosphinothioyloxy-l-thjo-Tenslofix NS phthalide was purified by column chromatography usingShellsol A 100 methylene chloride and silica gel. M.P. 39-40.5 C. Yield(Where TeIlSlOfiX AS and TeHSlOfiX NS are both mlffed 57%. blends, butin different proportions, of polyethylene oxlde Analysis (percent byweight) .-Found: C, 41.5; H, 3.9; condensates and anionic alkylsulfonates and Shellsol A P, 10.5; S, 22.2. C H PS Q, requires: C, 41.4;H, 3,8; 1s a mixture of tnmethylbenzenes). P, 10.7; S, 22.05. EXAMPLEV11 EXAMPLE IV Insecticidal activity of the organophosphorus phthalidePreparation of 5-[methoxy(dimethylamino) phosphinoderivativesthioyloxylphthalide A 0.1% by weight solution in acetone of the compoundA solution of the sodium salt of 5-hydroxyphthalide 40 was prepared andtaken up in a micrometer syringe. Adult was prepared by dissolvingmetallic sodium (0.75 w.) female house flie (Musca dor nestz ca) wereanaesthetized in dry methanol v.) and adding S-hydroxyphthalide withcarbon dioxide and 1 microliter of the solution ap- (5 w.). The solventwas removed from this solution plied to the ventral abdomen of each fly.The treated flies under reduced pressure and the residue so obtained diswere then placed in glass jars, each contalnmg a small solved in amixture of methyl isobutyl ketone v.) 45 quantity of sugar as food forthe fi1es. Twenty-four hours and dry ethanol (25 v.). The resultingsolution was heated later the number of dead and moribund files wasrecorded.

TABLE 1 M ltln Compound point: C Analysis (percent by weight)ii-dimethoxyphosphinothioyloxy phthalide WL13375 101 5 103 {ggpng g iflg ga lg, gig- 3 c -dimethoxyphosphinothioyloxy phthalide WL17470 8&88{ggfin c l g tmifi g; 5, 11 115?- 7 7-dimethoxyphosphinothioyloxyphthalide WL17617 H3 g u g H; B g? 1: 11 s, 1'1 7 O I -diet oxyphosp otoy o y p t a de W 36438 1 -:l-

10.6. 5-diethoxyphosphinothioyloxy phthalide in Table 38 540 5{@gpradgf, 1%210 3 c e ediethoxyphosphinothioyloxy-l-thiophthalide inTable 66 H8 {g0ilI1g;t(e3&4z5j 45H, 51.5); f, 9;; ,82%1.20 2 ac5-djmethoxyphosphinothioyloxy-G-methoxyphthalide WL17523 119422 tca lifigil, 331; S2, 5

c e:, 3-(lichloromethylene-fi-dimethoxyphosphinothioyloxy phthalide 61{ggflnutllgtq 3(8). g3, 2(J51, $11.4; 0P6 61 9.8 74-chloro-5-(dlethoxyphosphinyloxy)-6methoxyphthalide 121 5423 5goimdgtl, 9;; S18, lli .10 2

acu e z 3-meth171+(dimethoxyphosphinothioyloxy) phtha1lde (1)ggpnlgeitg3a4od1 1IgI, 4E l1,51()l. 6;1%,8110.11 1

c 2 y i 1 -I e 0 y(et 0 y)p osp o oy o ylp de (2) 5 1 1 1 11. P S 51. 1.1 l t o ywt y)p p ot ioyloxyl l-t iophthalide (3) gl i gflgio S 2:15- 1I'Hmethoxyfisopropyloxy)phosphinothioyloxylphthalide 7&81 $41525}? 5. 1;s ,1b 1.

c 5(dilsopropoxyphospbinothloyloxy)-l-thiophthalide 934M 5 {gginllilittlafilz 181, 51.15; g, 9.11; 3,4120.1g 5 c e:5-[methoxy-(2-methoxyethoxy)phosphinothloyloxy]phthalide (1) 03213; g,450 -4l?5l,3 g; 1457941) $9,810.82.10 1

a fi-[ y( y y)p p y lp (1) 8 I 2. 1 15-[methoxy(ethoxycarbonylmethoxy)phosphinothioyloxylphthalide (a)gl11(.:1u(};g,:'4:g,;)3

1 Colorless oil. 2 Pale yellow oil. 3 Yellow oil.

The results of the above tests are summarized in Table 2, where Adenotes 100% kill, B some kill and C no kill of the test insects.

sulfonic acids containing at least 10 carbon atoms in the molecule, forexample, sodium lauryl sulfate, sodium secondary alkyl sulfates, sodiumsalts of sulfonated castor oil, and sodium alkylaryl sulfonates such assodium dodecylbenzene sulfonate.

The compositions of the invention may be formulated as wetta'blepowders, dusts, granules, solutions, emulsifi able concentrates andemulsions.

The compositions of the invention may contain other ingredients, forexample, protective colloids such as gelatin, glue, casein, gums andpolyvinyl alcohol; sodium polyphosphates; cellulose ethers; stabilizerssuch as ethylene TABLE 2 M usca Aedes Phaedon Plutella AcyrthosiphonTetranychus Compound domestica aegypti cochleariae maculipeqmzs pisumtelarius 5-dimethoxyphosphinothioyloxyphthalide A A A A A i B5dimethoxyphosphinothioyloxy-l-thiophthalide A A A A A B5'diethoxyphosphinothioyloxyphthalide A C A A A O4-bromo-5dimethoxyphosphinothioyloxy-phthalide B B A A A C5-diethoxyphosphinothioyloxy-l-thiophthalide A A A A A A5-[methoxy(ethoxy)phosphinothioyloxy]-1-thiophthalide A A A A A A5[n1ethoxy(ethoxy) phosphinothioyloxy phthalide A A A A A A5-[n1ethoxy-(Z-methoxyethoxy) ph osphinothioyloxylphthalide C A A A A AThe compounds of the invention may be used in the manner known fororganophosphorus insecticides, that is to say, they may be applied inadmixture with an inert diluent or with both an inert diluent and asurface active agent. The invention therefore includes insecticidalcompositions which comprise compounds of the invention together with acarrier, or a surface active agent, or both a carrier and a surfaceactive agent.

The term carrier as used herein means a material, which may be inorganicor organic and of synthetic or natural origin, with which the activecompound is mixed or formulated to facilitate its application to theplant, seed, soil or other object to be treated or its storage,transport or handling. The carrier may be a solid or a fluid. Any of thematerials usually applied in formulating herbicides or insecticides maybe used as carrier.

Examples of suitable solid carriers are silicates, clays, for examplekaolinite clay, synthetic hydrated silicon oxides, synthetic calciumsilicates, elements such as for example, carbon and sulfur, natural andsynthetic resins such as for example, coumarone resins, rosin, copal,shellac, dammar, polyvinyl chloride and styrene polymers and copolymers,solid polychlorophenols, bitumen, asphaltite, waxes such as for example,beeswax, parafiin wax, montan wax and chlorinated mineral waxes, andsolid fertilizers, for example superphosphates.

Examples of suitable fluid carriers are water, alcohols, such as forexample, isopropanol, ketones such as for example, acetone, methyl ethylketone, methyl isobutyl ketone and cyclohexanone, ethers, aromatichydrocarbons such as for example, benzene and toluene, petroleumfractions such as for example, kerosine, chlorinated hydrocarbons, suchas for example, carbon tetrachloride, including liquified normallyvaporous or gaseous organic compounds. Mixtures of different liquids areoften suitable.

The surface active agent may be a wetting agent, an emulsifying agent ora dispersing agent; it may be nonionic or ionic. Any of the surfaceactive agents usually applied in formulating herbicides or insecticidesmay be used. Examples of suitable surface active agents are the sodiumor calcium salts of polyacrylic acids, the condensation products offatty acids or aliphatic amines or amides containing at least 12 carbonatoms in the molecule with ethylene oxide and/or propylene oxide;partial esters of the above fatty acids with glycerol, sonbitan, sucroseor pentaerythritol; condensation products of alkyl phenols, for examplep-octylphenol or p-octylcresol, with ethylene oxide and/or propyleneoxide; sulfates or sulfonates of these condensation products; and alkalimetal salts, preferably sodium salts, or sulfuric acid esters or diaminetetra-acetic acid; other herbicides or pesticides; and stickers, forexample non-volatile oils.

Aqueous dispersions and emulsions, for example, compositions obtained:by diluting a wettable powder or an emulsifiable concentrate accordingto the invention with water also lie within the scope of the presentinvention. The said emulsions may be of the water-in-oil or of theoil-in-water type, and may have a thick, mayonnaiselike consistency.

Other typical species of the compounds of the invention include:

S-[ethoxy (methylamino)phosphinothioyloxy] l thiophthalide;

S-[methoxy (amino)phosphinothioyloxy] phthalide;

5 [ethoxy (methylamino)phosphinothioyloxy] 1 thiophthalide;

5-[di(2-chloroethoxy)phosphinothioyloxy] phthalide;

5 [tetramethyldiaminophosphinothioyloxy]-l-thiophthalide.

We claim as our invention: 1. A phosphorus ester of the formula whereinR and R each independently represents a member of the group consistingof alkoxy, bromo-substituted alkoxy and chloro-substituted alkoxy,alkenyloxy, amino, alkylamino, dialkylamino, alkoxyalkoxy andalkoxycarbonylalkoxy, in which each alkyl, alkoxy, and alkenyl moietycontains from one to four carbons, R" and R each independentlyrepresents a member of the group consisting of hydrogen, alkyl,bromo-substituted alkyl and chloro-substituted alkyl wherein each alkylgroup contains from one to four carbon atoms, with the proviso that Rand R together can represent a member of the group consisting ofalkylidene bromo-substituted alkylidene and chloro-substitutedalkylidene wherein each alkylidene group contains from one to fourcarbon atoms, X and Y each independently represents a member of thegroup consisting of sulfur and oxygen, Z represents a member of thegroup consisting of alkoxy of from 1 to 4 carbon atoms, chlorine andbromine, and n is a whole number from zero to three.

2. A phosphorus ester according to claim 1 wherein R and R each isunsubstituted alkoxy of from 1 to 3 carbon 7 8 atoms, R" and R each ishydrogen, X and Y each is 8. A phosphorus ester according to claim 3wherein sulfur, and n is zero. R and R each is methoxy.

3. A phosphorus ester according to claim 1 wherein R and R each isunsubstituted alkoxy of from 1 to 3 References Cited carbon atoms, R"and R" each is hydrogen, X 1s sulfur, 5 FOREIGN PATENTS Y is oxygen andn is zero.

4. A phosphorus ester according to claim 2 wherein R and R each isethoxy.

5. A phosphorus ester according to claim 2 wherein 1,086,048 10/1967Great Britain.

ALEX MAZEL, Primary Examiner R is methoxy and R is ethoxy. 10 ANNE MARIET. TIGHE, Assistant Examiner 6. A phosphorus ester according to claim 3wherein R is methoxy and R is ethoxy. US. Cl. X.R.

7. A phosphorus ester according to claim 2 wherein 4 4 R and R each ismethoxy.

